Production of artificial textile materials, films, and other shaped articles having a basis of a polymerized vinyl ester



Patented l, 1

rrronuc'rrou or ARTIFICIAL TEXTILE MA- AND. o'rmiznv SHAPED TEBIALS, FEMS,

ARTICLES HAVING A BASIS MERIZEDVINYLESTEB erce Roberts and Edgar Bert Johnson,

' Robert on 1A row- Spon on, near .Derby, and Michael Antony Young, Bristol, England, assignors to Celanese Corporation ware of America, acorporation of Dela- No Drawing. Application October- 23, 1941, Serial No. 416,212. In Great Britain March 4,1941

3 (o1. zoo-32) This invention relates to the production of artificial. textile.materials,. e. g. filaments, til 5 and other shapedarticleshaving a basis-o 'a l polymerized vinyl ester.

In forming filaments and the like from high" molecular weight polymerization products of mixtures of a vinyl halide and avinyl ester of an aliphatic acid it has hitherto been proposed to shapeand set acetone solutions of the-products.

However, we have found that such so-called solutions are unsatisfactory for the purpose of producing uniform products, since they lack homogeneity, even at'temperatures of the order of the boiling point of acetone. We have further found that this defectcan be effectively overcome by employing, as solvent of compositions from which I filaments and the like are to be formed, a mix- -turecomprising acetone and oneor more other organic liquids, which, need not zit-ordinary. tempratures be solvents .for the polymerization product. I I -.,-Accordihg to the invention, therefore, artificial textile materials; films and other shaped articles are'produced by a process which comprises shaping a solution of a po merized mixture of a vinyl halide and a vinyl ester of an aliphatic acid in a mixture of .acetone and another organic liquid; and setting the shaped materials by evaporation of solventtherefrom.

Preferably the additional organic liquids are such as produce, in admixture with acetone, solu. ,tions of the polymer having lower viscosity than solutions of equal concentration in substantially pureacetone. These additional liquids advantageously possess a solvent or-swelling action for the polymer and are referred to in the appended claims as swelling agents. Particularly suitable'liquids are, for example, aromatic hydrocarbons, especially benzene, toluene and xylene, and aliphatic fathers, especially cyclic ethers, e. g. ethylene methylene ether and dioxane.

. and 30-20 parts by. volume of benzene, especially a 75/25 mixture; or of about 45-60 ,parts by volume ofTaceton'e and 55-40 parts by volume of Thus, very satisfactory solvent media" consist of about '70-80-parts by volume of acetone high-boiling or relatively non-volatile agents may contain about 5-12 or 15% or more thereof, based on the weight of the polymer to be dissolved in the mixture.

The invention is of the greatest importance in connection with the spinning of filaments from high molecular weight products, e. g. products of molecular weightabove 10,000 or 12,000 and preferably substantially above 15,000, e. g. 22,000 to 25,0000! more, formed by polymerizing a mixture comprising a large proportion of the .vinylhalide, especially the chloride, in relation tothe proportion of the vinyl ester of an organic acid. The esters of organic acids are preferably those of lower fatty acids, among which acetic, propicnic and butyric acids are important examples;

esters of substitution derivatives of these acids,

r e. g. lbwer halogen-fatty acids, may also be employed. Particularly. suitable polymerization products are such as may be produced from ixtures of 80 or 85 to95 or 9'7.%-by weight'of nyl chloridefthe remainder of the mixture being vinyl acetate. If desired, more thanone halide and/or ore than one ester of anorganic ac 'may-be" resent. in the polymer.

The concentrationof polymer in the solution "to be spun is preferably between about 15% and -30%,.especially' about 25%. The solution. may be prepared by kneading a quantity of the polymer with solvent mixture, advantageously at elevated temperature, and then diluting or concentrating sired concentration. Alternatively, the polymer may be kneaded with acetone and the other component or components-of the solvent, mixture may then be added, or vice versa, adiustments of concentration being made at anystage as desired.

what elevated temperature; and freed from air, e. 8- by being left to stand at elevated temperatune for filter the solution while relatively highly diluted,

1 so as to facilitatethefiltration, -and to concenby the usual evaporative method, with the niodific'ation that the extruded materials, after setethylene methylene ether, especially 'a -50/ ,50 n'iixture. Other suitable liquidspossessingswellin power for the polymer are, for example, ethylene dichloridejmethylene chloride and certain highboiling or substantiallynon-vdlatile'agents such as, for example, cyclohexanone, methyfcyclohexanone, c'yclohexanol oxalate dimethyiecygos ahe'anol oxalate, and methyl cyclbhexanol .rate. suitable solvent mixtures comprising ture of the evaporative medium may be, for ex- Ample, of the order of as"v c. and the spinning speed aboutmetres per minute, though these such 6 conditions will depend in part upon the composi- 'trate by evaporation thereafter.

Filaments maybe formed from such solutions ting-are passed. through an aqueous'bath, which- 3 eithericold or hot, e. g. at or above 50 I may be v e 0., beforebeing wound up. v winding. may take place im the aqueous bath. itself. The tempera the product, as necessary, to bring it to the de- The solution may be filtered, preferably at some several hours. 'It'may be desirable to 2 tion ofthe solution and the diameter of the extrusion orifices as well as upon the length of travel through the evaporative medium. Films and other shaped articles may be produced in a more of their original length in one or more stages. While this operation is preferably effected according to the process of U. S. application S. No. 416,213 filed October 23, 1941, it may also be carried out while the materials are merely wetted with hot or cold water, with or without a wetting agent. r a

Filamentary p oducts formed according to the invention may be twisted together to form yarns which maybe subjected to knitting, weaving or other fabric-forming operations. The regularity of the filamentary products leads to a high degreeof evenness in fabrics formed from them.

Example 1 I A polymerized mixture of 91% of vinyl chloride and 9% vinyl acetate having a molecular weight of about 24,400 (as determined by viscosity measlength by 60% to 180% or even up to room. or

urement); is dissolved in a mixture of 96.6% by weight of acetone and 3.3% by weight of dimethyl cyclohexanol oxalate to form a' 25% solution.

'After filtration and deaeration, the solution is ex- The polymer described in Example 1 is dissolved I in a mixture of 75 parts by volume of acetone and 25 parts of benzene to form a 25% solution. Spinning and winding is carried out as in Example 1.

Example-3 1 ficial textile materials, films and other shaped articles 'by the' extrusion thereof ,through an orifice into a setting medium, comprising a polymerized. mixture of vinyl chloride and vinyl acetate in a mixture consisting of from 45 to 60% by volume of acetone and from 55 to 40% by volume of ethylene methylene ether, said polymerized mixture being present in said solution in a concentration of 15 to 30%.

2. A solution for use in the production of artificial textile materials, films and other shaped articles by the extrusion thereofthrough an orifice into a setting medium, comprising a polymerized mixture of 80 to 97% by weight of vinyl chloride.

and 20' to 3% by weight of vinyl acetate in a mixture consisting orfron; to 60% by volume of acetone and from to 40% by volume of ethylene methylene ether, said polymerized mix-.

ture being present in said solution in a concentration of 15 to 30%. Y

3. A solution for use in the production of artificial textile materials, films and other shaped,

, sisting of from 45 toby volume of acetone and from 55 to40% by volume of ethylene methylene ether, ,said polymerized mixture being present in said solutionin a concentration of 25%.

ROBERT PIERCE ROBERTS;

EDGAR BERT JOHNSON. MICHAEL ANTONY YOUNG. 

